CN107207661B - Ethylene/alpha-olefin copolymer having excellent processability and surface characteristics - Google Patents

Ethylene/alpha-olefin copolymer having excellent processability and surface characteristics Download PDF

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CN107207661B
CN107207661B CN201680007527.4A CN201680007527A CN107207661B CN 107207661 B CN107207661 B CN 107207661B CN 201680007527 A CN201680007527 A CN 201680007527A CN 107207661 B CN107207661 B CN 107207661B
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ethylene
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CN107207661A (en
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承裕泽
宣淳浩
曺柗
崔二永
李琪树
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LG Chem Ltd
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Abstract

The present invention relates to an ethylene/alpha-olefin copolymer. The ethylene/alpha-olefin copolymer according to the present invention has excellent processability and surface characteristics, and thus can be used to manufacture various products.

Description

Ethylene/alpha-olefin copolymer having excellent processability and surface characteristics
Technical Field
Cross Reference to Related Applications
This application claims the benefit of priority from korean patent application No. 10-2015-.
The present invention relates to an ethylene/alpha-olefin copolymer having excellent processability and surface characteristics.
Background
Olefin polymerization catalyst systems can be classified into ziegler-natta and metallocene catalyst systems, and these two high-activity catalyst systems have been developed according to their characteristics. Since the development in the fifties of the twentieth century, ziegler-natta catalysts have been widely used in existing commercial processes. However, since the Ziegler-Natta catalyst is a multi-active-site catalyst in which a plurality of active sites are mixed, it has a characteristic that the molecular weight distribution of the polymer is broad. In addition, since the composition distribution of the comonomer is not uniform, there is a problem in that desired physical properties are secured.
Meanwhile, the metallocene catalyst comprises a combination of a main catalyst whose main component is a transition metal compound and an organometallic compound cocatalyst whose main component is aluminum. This catalyst is a single-site catalyst, which is a homogeneous complex catalyst and, depending on the single-site character, provides polymers with narrow molecular weight distribution and uniform comonomer composition distribution. By changing the ligand structure of the catalyst and the polymerization conditions, the metallocene catalyst has the characteristics that the stereoregularity, copolymerization properties, molecular weight, crystallinity and the like of the obtained polymer can be controlled.
U.S. Pat. No. 5,914,289 discloses a method for controlling molecular weight and molecular weight distribution of a polymer using metallocene catalysts separately supported on a carrier. However, a large amount of solvent and a long time are required to prepare the supported catalyst, and the process of supporting the metallocene catalyst on each support is cumbersome.
Korean patent application No. 10-2003-0012308 discloses a method of controlling the molecular weight distribution of a polymer by changing the combination of catalysts in a reactor and performing polymerization by supporting a dinuclear metallocene catalyst and a mononuclear metallocene catalyst on a carrier having an activator. However, this method has a limitation in achieving the properties of each catalyst at the same time. In addition, it has a disadvantage that the metallocene catalyst is partially detached from the supported components of the catalyst to cause fouling in the reactor.
Therefore, in order to overcome the above disadvantages, it is required to develop a method for preparing an olefin polymer having desired physical properties by easily preparing a supported hybrid metallocene catalyst having excellent activity.
On the other hand, linear low density polyethylene is produced by copolymerizing ethylene and α -olefin using a polymerization catalyst at low pressure. Thus, it is a resin with a narrow molecular weight distribution and short chain branches of a certain length, but no long chain branches. The linear low density polyethylene film has high strength and elongation at break in addition to the properties of general polyethylene, and exhibits excellent tear strength, drop impact strength, and the like. This has led to an increase in the use of stretched films, overlapped films, and the like, which are difficult to apply to existing low density polyethylene or high density polyethylene.
However, linear low density polyethylene using 1-butene or 1-hexene as a comonomer is mainly produced in a single gas phase reactor or a single loop slurry reactor and has high productivity compared to the process using 1-octene comonomer. However, these products have limitations in terms of catalyst technology and process technology. Therefore, they have problems in that their physical properties are much worse than those using a 1-octene comonomer, the molecular weight distribution is narrow, and the processability is poor. Many studies have been made to improve these defects.
U.S. Pat. No. 4,935,474 describes a process for preparing polyethylene having a broad molecular weight distribution by using two or more metallocene compounds. U.S. Pat. No. 6,828,394 discloses a method for preparing polyethylene excellent in processability and particularly suitable for films by using a catalyst system comprising a poor comonomer incorporating catalyst compound and a good comonomer incorporating catalyst compound. Further, U.S. Pat. No. 6,841,631 and U.S. Pat. No. 6,894,128 describe the preparation of polyethylene having a bimodal or multimodal molecular weight distribution by using a metallocene-type catalyst comprising at least two metal compounds, and thus can be used in various applications such as films, blow molding and forming, and pipes. However, although these products have improved processability, there is still a problem that the dispersion state per molecular weight within a unit particle is not uniform, and thus the extruded appearance is rough and the physical properties are unstable even under relatively good extrusion conditions.
In view of the above, there is a continuing need to produce quality products having a balance between physical properties and processability. In particular, there is a further need for polyethylene copolymers having excellent processability.
Disclosure of Invention
[ problem ] to
In order to solve the problems of the prior art, an object of the present invention is to provide an ethylene/α -olefin copolymer having excellent environmental stress cracking resistance.
[ solution ]
In order to achieve the above object, the present invention provides an ethylene/α -olefin copolymer satisfying the following conditions:
a weight average molecular weight (g/mol) of 50,000 to 150,000,
a molecular weight distribution (Mw/Mn) of 3 to 8,
a density (g/cm) of 0.940 to 0.9703)，
A spherulite diameter of 20 μm or less, and
a crystallization half time measured at 123 ℃ of 6 minutes or less.
Ethylene/alpha-copolymers are semi-crystalline polymers and the surface characteristics of these polymers are mainly influenced by the crystalline structure. Most polymer chains are not linearly extended but exist in a shape folded at a short distance. These folded chains aggregate into bundles to form platelets, while spherulites are formed by the three-dimensional growth of platelets (lamellars). In particular, the spherulites have a great influence on the surface characteristics of the polymer. Reducing the spherulite size can impart better surface characteristics to the polymer.
The structure of spherulites is influenced by various factors such as the molecular weight of the polymer, the molecular weight distribution, the amount of comonomer, and the comonomer distribution. Generally, it is known that as the molecular weight of a polymer increases and the amount of comonomer increases, the size of spherulites decreases. However, in this case, the melt index, density, etc. increase, and thus a polymer having desired properties cannot be produced.
On the other hand, the crystallization rate of a polymer is related to the processability of the polymer, and the faster the crystallization rate, the more advantageous the processing of the polymer. Further, if the crystallization speed is high, the size of the crystal can be miniaturized, and thus the size of the spherulite can be reduced.
In this regard, the present invention is characterized in that the generation of LCB (long chain branching) is induced in an ethylene/α -olefin copolymer using a catalyst described later, thereby reducing the size of spherulites and increasing the crystallization speed. Specifically, the ethylene/alpha-olefin copolymer according to the present invention is characterized in that the diameter of spherulites is 20 μm or less and the half-crystallization time measured at 123 ℃ is 6 minutes or less, preferably 5 minutes or less.
As in the embodiment of the present invention described below, the diameter of spherulites can be determined by observing the surface of the ethylene/α -olefin copolymer with a microscope or the like. Specifically, the ethylene/α -olefin copolymer was completely melted at 190 ℃ and then reached the crystallization temperature at a rate of 10 ℃/min, and then the diameter of spherulites was measured. Here, the diameter of the spherulites is a size at which the respective spherulites overlap according to growth of the spherulites.
In addition, Differential Scanning Calorimetry (DSC) was used to measure the half-crystallization time, which is the time at which the ethylene/alpha-olefin copolymer completely melts at 190 ℃ and then quenched (80 ℃/min) until half the peak of the heat that occurred after the crystallization temperature (123 ℃) was held for 1 hour.
According to an embodiment of the present invention, when the generation of LCB (long chain branching) is induced in the ethylene/α -olefin copolymer using the later-described catalyst, the size of spherulites is significantly small and the semi-crystallization speed is significantly faster than that of the ethylene/α -olefin copolymer having the same molecular weight, as compared to the case when the later-described catalyst is not used to induce the generation of LCB (long chain branching) in the ethylene/α -olefin copolymer.
Further, preferably, the MFRR of the ethylene/alpha-olefin copolymer2.16(melt flow index measured at 190 ℃ under a load of 2.16kg according to ASTM D1238) of from 0.5 to 10, more preferably from 4 to 8.
Furthermore, preferably, ethyleneMFRR for/alpha-olefin copolymers5/2.16(the value of the melt flow index measured at 190 ℃ under a load of 5kg divided by the melt flow index measured at 190 ℃ under a load of 2.16kg, according to ASTM D1238) is from 3 to 8, more preferably from 3 to 4.
In the ethylene/α -olefin copolymer according to the present invention, specific examples of the α -olefin monomer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like, and two or more of them may also be used. Preferably, 1-butene may be used as the alpha-olefin monomer.
The content of the α -olefin as the comonomer in the ethylene/α -olefin copolymer is not particularly limited, and may be appropriately selected depending on the use, purpose, and the like of the copolymer. More specifically, it may be more than 0 mol% and less than 99 mol%.
The ethylene/alpha-olefin copolymer described above may be prepared using a metallocene catalyst. The metallocene catalyst that may be used may be one or more first metallocene compounds represented by the following chemical formula 1; and one or more second metallocene compounds selected from the group consisting of compounds represented by the following chemical formulas 3 to 5:
[ chemical formula 1]
Figure GDA0002655241330000041
In the chemical formula 1, the first and second,
a is hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-20Aryl radical, C7-20Alkylaryl group, C7-20Arylalkyl radical, C1-20Alkoxy radical, C2-20Alkoxyalkyl group, C3-20Heterocycloalkyl or C5-20A heteroaryl group;
d is-O-, -S-, -N (R) -or-Si (R) (R ') -, wherein R and R' are the same or different from each other and are each independently hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl or C6-20An aryl group;
l is C1-10A linear or branched alkylene group;
b is carbon, silicon or germanium;
q is hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-20Aryl radical, C7-20Alkylaryl or C7-20An arylalkyl group;
m is a group 4 transition metal;
X1and X2Are identical or different from each other and are each independently halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-20Aryl, nitro, amido, C1-20Alkylsilyl group, C1-20Alkoxy or C1-20Sulfonate groups (sulfonates);
C1and C2Are the same or different from each other, and are each independently represented by one of the following chemical formulae 2a, 2b or 2C, provided that C is excluded1And C2Both in the case of chemical formula 2c,
[ chemical formula 2a ]
Figure GDA0002655241330000051
[ chemical formula 2b ]
Figure GDA0002655241330000052
[ chemical formula 2c ]
Figure GDA0002655241330000061
In chemical formulas 2a, 2b and 2c, R1To R17And R1' to R9' the same or different from each other, and each independently is hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C1-20Alkylsilyl group, C1-20Silylalkyl group, C1-20Alkoxysilyl group, C1-20Alkoxy radical, C6-20Aryl radical, C7-20Alkylaryl or C7-20Arylalkyl, and two or more R adjacent to each other10To R17Are linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
[ chemical formula 3]
(Cp1Ra)n(Cp2Rb)M1Z1 3-n
In the chemical formula 3, the first and second,
M1is a group 4 transition metal;
Cp1and Cp2The same or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl group, indenyl group, 4,5,6, 7-tetrahydro-1-indenyl group and fluorenyl group, which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
Raand RbAre identical or different from each other and are each independently hydrogen, C1-20Alkyl radical, C1-10Alkoxy radical, C2-20Alkoxyalkyl group, C6-20Aryl radical, C6-10Aryloxy radical, C2-20Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C8-40Arylalkenyl or C2-10An alkynyl group;
Z1is a halogen atom, C1-20Alkyl radical, C2-10Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C6-20Aryl, substituted or unsubstituted C1-20Alkylene group, substituted or unsubstituted amino group, C2-20Alkyl alkoxy or C7-40An arylalkoxy group;
n is 1 or 0;
[ chemical formula 4]
(Cp3Rc)mB1(Cp4Rd)M2Z2 3-m
In the chemical formula 4, the first and second organic solvents,
M2is a group 4 transition metal;
Cp3and Cp4Are connected with each otherThe same or different, and each independently is any one selected from the group consisting of cyclopentadienyl group, indenyl group, 4,5,6, 7-tetrahydro-1-indenyl group and fluorenyl group, which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
Rcand RdAre identical or different from each other and are each independently hydrogen, C1-20Alkyl radical, C1-10Alkoxy radical, C2-20Alkoxyalkyl group, C6-20Aryl radical, C6-10Aryloxy radical, C2-20Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C8-40Arylalkenyl or C2-10An alkynyl group;
Z2is a halogen atom, C1-20Alkyl radical, C2-10Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C6-20Aryl, substituted or unsubstituted C1-20Alkylene group, substituted or unsubstituted amino group, C2-20Alkyl alkoxy or C7-40An arylalkoxy group;
B1to make Cp3RcRing and Cp4RdRing crosslinking or bringing together a Cp4RdRing and M2At least one of cross-linked free radical-containing carbon, germanium, silicon, phosphorus, or nitrogen atoms, combinations thereof;
m is 1 or 0;
[ chemical formula 5]
(Cp5Re)B2(J)M3Z3 2
In the chemical formula 5, the first and second organic solvents,
M3is a group 4 transition metal;
Cp5is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6, 7-tetrahydro-1-indenyl and fluorenyl, which may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
Reis hydrogen, C1-20Alkyl radical, C1-10Alkoxy radical, C2-20Alkoxyalkyl group, C6-20Aryl radical, C6-10Aryloxy radical, C2-20Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C8-40Arylalkenyl or C2-10An alkynyl group;
Z3is a halogen atom, C1-20Alkyl radical, C2-10Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C6-20Aryl, substituted or unsubstituted C1-20Alkylene group, substituted or unsubstituted amino group, C2-20Alkyl alkoxy or C7-40An arylalkoxy group;
B2to make Cp5ReAt least one of a radical-containing carbon, germanium, silicon, phosphorus, or nitrogen atom, or a combination thereof, with the ring crosslinked with J;
j is selected from NRf、O、PRfAnd any of S, and RfIs C1-20Alkyl, aryl, substituted alkyl or substituted aryl.
The substituents of chemical formulas 1, 3,4 and 5 will be more specifically described as follows.
C1-20The alkyl group includes a straight chain or branched chain alkyl group, and specific examples thereof include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like.
C2-20The alkenyl group includes a straight or branched alkenyl group, and specific examples thereof include, but are not limited to, allyl, vinyl, propenyl, butenyl, pentenyl, and the like.
C6-20The aryl group includes monocyclic or fused ring type aryl groups, and specific examples thereof include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, fluorenyl and the like.
C5-20The heteroaryl group includes monocyclic or fused ring type heteroaryl groups, and specific examples thereof include carbazolyl, pyridyl, quinoline, isoquinoline, thienyl, furyl, imidazole, oxazolyl, thiazolyl, triazine, tetrahydropyranyl, tetrahydrofuranyl and the like, but are not limited thereto.
C1-20The alkoxy group includes methoxy, ethoxy, phenoxy, cyclohexyloxy, etc., but is not limited thereto.
Examples of the group 4 transition metal include titanium, zirconium, hafnium, etc., but are not limited thereto.
R in chemical formulas 2a, 2b and 2c1To R17And R1' to R9' are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, phenyl, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, trimethylsilylmethyl, methoxy, or ethoxy, but are not limited thereto.
L in chemical formula 1 is more preferably straight or branched C4-8Alkylene groups, but are not limited thereto. Furthermore, the alkylene group may be substituted by C1-20Alkyl radical, C2-20Alkenyl or C6-20Aryl is substituted or unsubstituted.
Further, a in chemical formula 1 is preferably hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, methoxymethyl, t-butoxymethyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl, tetrahydropyranyl or tetrahydrofuranyl, but is not limited thereto.
Further, B in chemical formula 1 is preferably silicon, but is not limited thereto.
The first metallocene compound of chemical formula 1 forms a structure in which an indenoindole derivative and/or a fluorene derivative is crosslinked via a bridge, and has an unshared electron pair that can serve as a lewis base in a ligand structure, thereby exhibiting high polymerization activity even when supported on the surface of a carrier having lewis acid properties. In addition, the activity is high by including an electron-rich indenoindolyl group and/or fluorenyl group, and not only the hydrogen reactivity is low but also the high activity is maintained even in the presence of hydrogen due to appropriate steric hindrance and electronic effects of the ligand. In addition, the beta-hydrogens of the polymer chains (where the nitrogen atom of the indenoindole derivative grows) are stabilized by hydrogen bonding to inhibit beta-hydrogen elimination, thereby polymerizing to form the ultra-high molecular weight olefin polymer.
According to an embodiment of the present invention, specific examples of the compound represented by chemical formula 2a may include a compound represented by any one of the following structural formulae, but the present invention is not limited thereto.
Figure GDA0002655241330000081
Figure GDA0002655241330000091
According to an embodiment of the present invention, specific examples of the compound represented by chemical formula 2b may include a compound represented by one of the following structural formulae, but the present invention is not limited thereto.
Figure GDA0002655241330000092
Figure GDA0002655241330000101
According to an embodiment of the present invention, the compound represented by chemical formula 2c may include a compound represented by one of the following structural formulae, but the present invention is not limited thereto.
Figure GDA0002655241330000102
According to an embodiment of the present invention, specific examples of the first metallocene compound represented by chemical formula 1 may include a compound represented by one of the following structural formulae, but are not limited thereto.
Figure GDA0002655241330000103
Figure GDA0002655241330000111
Figure GDA0002655241330000121
The first metallocene compound of chemical formula 1 has excellent activity and can polymerize an ethylene/α -olefin copolymer having a high molecular weight. In particular, since it can exhibit high polymerization activity even when it is used in a state of being supported on a carrier, it is possible to produce an ethylene/α -olefin copolymer having an ultrahigh molecular weight.
Further, even if the polymerization reaction is carried out in the presence of hydrogen in order to produce an ethylene/α -olefin copolymer having both a high molecular weight and a broad molecular weight distribution, the first metallocene compound of chemical formula 1 according to the present invention exhibits low hydrogen reactivity, and thus it is still possible to polymerize an ethylene/α -olefin copolymer having an ultra-high molecular weight with high activity. Therefore, even if it is used as a mixture with a catalyst having different characteristics, it is possible to produce an ethylene/α -olefin copolymer satisfying high molecular weight characteristics without decreasing the activity, thereby easily producing an ethylene/α -olefin copolymer having a broad molecular weight distribution while containing an ethylene/α -olefin copolymer having a high molecular weight.
The first metallocene compound of chemical formula 1 can be prepared by the following method: the ligand compound is prepared by linking an indenoindole derivative and/or a fluorene derivative via a bridging compound, and then metallation is performed by introducing a metal precursor compound thereto. The method for producing the first metallocene compound will be specifically described in the following examples.
The compound represented by chemical formula 3 may be, for example, a compound represented by one of the following structural formulae, but is not limited thereto.
Figure GDA0002655241330000131
In chemical formula 4, when m is 1, Cp is represented3RcRing and Cp4RdRing, or Cp4RdAnd M2Via B1A crosslinked structure, when m is 0, represents a structure of an uncrosslinked compound。
The compound represented by chemical formula 4 may be, for example, a compound represented by one of the following structural formulae, but is not limited thereto.
Figure GDA0002655241330000141
Figure GDA0002655241330000151
In addition, the compound represented by chemical formula 5 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
Figure GDA0002655241330000152
Figure GDA0002655241330000161
The metallocene catalyst used in the present invention may be one in which at least one of first metallocene compounds represented by chemical formula 1 and at least one of second metallocene compounds selected from compounds represented by chemical formulas 3 to 5 are supported together with a cocatalyst compound on a carrier.
In addition, the supported metallocene catalyst can induce the production of LCB (long chain branching) in the ethylene/α -olefin copolymer to be produced.
In the supported metallocene catalyst according to the present invention, the cocatalyst for activating the metallocene compound and supported on the carrier is an organometallic compound containing a group 13 metal, which is not particularly limited as long as it can be used for polymerizing olefins in the presence of a general metallocene catalyst.
Specifically, the promoter compound may include at least one of an aluminum-containing first promoter of the following chemical formula 6 and a boron-containing second promoter of the following chemical formula 7.
[ chemical formula 6]
-[Al(R18)-O-]k-
In chemical formula 6, R18Each independently a halogen, a halogen substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more,
[ chemical formula 7]
T+[BG4]-
In chemical formula 7, T+Is a +1 valent polyatomic ion, B is boron in a +3 valent oxidation state, and each G is independently selected from hydride, dialkylamido, halide, alkoxide, aryloxy, hydrocarbyl, halocarbyl, and halogen-substituted hydrocarbyl, wherein G has less than 20 carbon atoms, with the proviso that G is a halide at one or fewer positions.
By using the first and second co-catalysts as described above, the finally prepared polyolefin may have a more uniform molecular weight distribution, and at the same time, the polymerization activity may be improved.
The first cocatalyst of chemical formula 6 may be an alkylaluminoxane-based compound in which repeating units are combined into a linear, cyclic or net shape. Specific examples of the first cocatalyst include Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.
In addition, the second co-catalyst of chemical formula 7 may be a tri-substituted ammonium salt, a dialkyl ammonium salt, or a tri-substituted phosphate type borate compound. Specific examples of the second cocatalyst include borate-based compounds in the form of tri-substituted ammonium salts, such as trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (N-butyl) ammonium tetraphenylborate, methyltetradecylactadecylammonium tetraphenylborate, N-dimethylanilinium tetraphenylborate, N-diethylanilinium tetraphenylborate, N-dimethyl (2,4, 6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, methyldiocetradecylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, lithium salts of lithium, lithium salts of lithium, Tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N-dimethyl (2,4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, tri (N-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, dimethyl (tert-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N-dimethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N-diethylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (2,3,4, 6-tetrafluorophenyl) borate, or the like; borate-based compounds in the form of dialkyl ammonium salts, such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) borate; or borate-based compounds in the form of tri-substituted phosphonium salts, such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tris (2, 6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate.
In the supported metallocene catalyst according to the present invention, the first metallocene compound represented by chemical formula 1 or the second metallocene compound represented by chemical formulas 3 to 5 may contain the entire transition metal in a mass ratio to the support of 1:10 to 1: 1000. When the support and the metallocene compound are contained within the above-mentioned mass ratio range, an optimum shape can be provided. The mass ratio of the cocatalyst compound to the support may be 1:1 to 1: 100.
In the supported metallocene catalyst according to the present invention, as the support, a support containing hydroxyl groups on the surface thereof can be used, and preferably a support having a surface which is dried and removed of moisture and has highly reactive hydroxyl groups and siloxane groups can be used.
For example, silica-alumina, silica-magnesia, etc., which are dried at high temperature, can be usedMay typically contain oxides, carbonates, sulfates and nitrates, e.g. Na2O、K2CO3、BaSO4And Mg (NO)3)2。
The drying temperature of the support is preferably 200 ℃ to 800 ℃, more preferably 300 ℃ to 600 ℃, and most preferably 300 ℃ to 400 ℃. If the drying temperature of the support is below 200 ℃, too much moisture remains, so that the moisture on the surface reacts with the cocatalyst. If the drying temperature is higher than 800 ℃, the pores on the surface of the support are bonded to each other to reduce the surface area, and many hydroxyl groups are lost on the surface, leaving only siloxane groups. Therefore, it is not preferable because the reactive site with the cocatalyst is reduced.
The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the support can be controlled depending on the preparation method and conditions of the support, or drying conditions (e.g., temperature, time, degree of vacuum, spray drying, etc.).
If the amount of hydroxyl groups is less than 0.1mmol/g, the reaction sites with the cocatalyst decrease. If the amount of the hydroxyl group exceeds 10mmol/g, it may be caused by moisture in addition to the hydroxyl group present on the surface of the carrier particle, and is therefore undesirable.
On the other hand, the ethylene/α -olefin copolymer according to the present invention can be prepared by polymerizing ethylene and α -olefin in the presence of the supported metallocene catalyst described above.
The polymerization reaction may be carried out by copolymerizing ethylene and α -olefins using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
The polymerization temperature may be from about 25 ℃ to about 500 ℃, preferably from about 25 ℃ to about 200 ℃, more preferably from about 50 ℃ to about 150 ℃. Further, the polymerization pressure may be about 1Kgf/cm2To about 100Kgf/cm2Preferably about 1Kgf/cm2To about 50Kgf/cm2More preferably about 5Kgf/cm2To about 30Kgf/cm2。
The supported metallocene catalyst may be injected after being dissolved or diluted in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms (e.g., pentane, hexane, heptane, nonane, decane and isomers thereof), an aromatic hydrocarbon solvent (e.g., toluene and benzene) or a hydrocarbon solvent substituted with a chlorine atom (e.g., dichloromethane and chlorobenzene). It is preferable to use a solvent after treatment with a small amount of aluminum alkyl to remove a small amount of water, air, etc., which are catalyst poisons. It is also possible to carry out the reaction using additional cocatalysts.
The ethylene/α -olefin copolymer according to the present invention may be prepared by copolymerizing ethylene and α -olefin monomers using the catalyst of chemical formulae 3 to 5, which mainly polymerize low molecular weight polymer chains, and the catalyst of chemical formula 1, which mainly polymerizes high molecular weight polymer chains. Due to the interaction between these two or more catalysts, a polymer comprising a higher content of polymer chains in the high molecular weight region can be obtained while having a broad molecular weight distribution as a whole.
Advantageous effects
The ethylene/alpha-olefin copolymer according to the present invention has excellent processability and surface characteristics, and thus can be used for various products.
Drawings
Fig. 1 shows an observation image of spherulites of a polymer prepared in one embodiment of the present invention.
Fig. 2 and 3 show observation images of spherulites of the polymer prepared in the comparative example of the present invention.
Detailed Description
Hereinafter, preferred examples are provided for better understanding of the present invention. However, these examples are for illustrative purposes only, and the present invention is not limited by these examples.
Preparation of example 1
Step 1) preparation of ligand Compound
2g of fluorene was dissolved in 5mL of MTBE and 100mL of hexane and 5.5mL of a 2.5M n-BuLi solution in hexane was added dropwise to the dry ice/acetone bath and stirred at room temperature overnight. 3.6g of (6- (tert-butoxy) hexyl) dichloro (methyl) silane were dissolved in 50mL of hexane and the fluorene-Li slurry was transferred in 30 minutes under a dry ice/acetone bath and stirred at room temperature overnight. Simultaneously, 5, 8-twoMethyl-5, 10-dihydroindeno [1,2-b ]]Indole (12mmol, 2.8g) was dissolved in 60mL THF and 5.5mL of a 2.5M n-BuLi in hexane was added dropwise under a dry ice/acetone bath and stirred at room temperature overnight. NMR check of the reaction solution of fluorene and (6- (tert-butoxy) hexyl) dichloro (methyl) silane to confirm completion of the reaction, followed by transfer of 5, 8-dimethyl-5, 10-dihydroindeno [1,2-b ] under a dry ice/acetone bath]indole-Li solution. The mixture was stirred at room temperature overnight. After the reaction, the reaction mixture was extracted with ether/water and MgSO4Removing residual water from the organic layer to obtain ligand compound (Mw 597.90, 12mmol), and purifying by1H-NMR confirmed the production of two isomers.
1H NMR(500MHz,d6-benzene) 0.30 to-0.18 (3H, d),0.40(2H, m),0.65 to 1.45(8H, m),1.12(9H, d),2.36 to 2.40(3H, d),3.17(2H, m),3.41 to 3.43(3H, d),4.17 to 4.21(1H, d),4.34 to 4.38(1H, d),6.90 to 7.80(15H, m)
Step 2) preparation of metallocene Compound
7.2g (12mmol) of the ligand compound synthesized in step 1 were dissolved in 50mL of diethyl ether, and 11.5mL of a 2.5M n-BuLi hexane solution was added dropwise under a dry ice/acetone bath and stirred at room temperature overnight. The mixture was dried in vacuo to give a viscous oil with a brown color. The oil was dissolved in toluene to give a slurry. Preparation of ZrCl4(THF)2And toluene (50mL) was added thereto to prepare a slurry. Transferring ZrCl under a Dry Ice/acetone bath4(THF)2(50mL) of a toluene slurry. The color changed to purple as the mixture was stirred at room temperature overnight. The reaction solution was filtered to remove LiCl. The filtrate was dried in vacuo to remove toluene, hexane was added thereto, and the mixture was sonicated for 1 hour. The slurry was filtered to give 6g of a metallocene compound (Mw 758.02, 7.92mmol, yield 66 mol%) with a deep purple color as a filtered solid. By passing1Two isomers were observed by H-NMR.
1H NMR(500MHz,CDCl3):1.19(9H,d),1.71(3H,d),1.50～1.70(4H,m),1.79(2H,m),1.98～2.19(4H,m),2.58(3H,s),3.38(2H,m),3.91(3H,d),6.66～7.88(15H,m)
Preparation of example 2
Preparation of tert-butyl-O- (CH) using 6-chlorohexanol was performed as described in Tetrahedron Lett.2951(1988)2)6-Cl, then with NaCp to give tert-butyl-O- (CH)2)6-C5H5(yield 60%, boiling point 80 ℃ C./0.1 mmHg).
Furthermore, tert-butyl-O- (CH) is reacted at-78 deg.C2)6-C5H5Dissolved in THF, n-BuLi was slowly added thereto, and the mixture was warmed to room temperature and then reacted for 8 hours. The lithium salt solution thus prepared was slowly added to ZrCl again at a temperature of-78 deg.C4(THF)2(1.70g, 4.50mmol)/THF (30mL) and the mixture was allowed to react further at room temperature for 6 hours.
All volatile materials were dried under vacuum, and hexane solvent was added to the resulting oily liquid material, followed by filtration. The filtrate was dried in vacuo and hexane was added to induce precipitation at low temperature (-20 ℃). The resulting precipitate was filtered at low temperature to give [ tBu-O- (CH) as a white solid2)6-C5H4]2ZrCl2Compound (yield 92%).
1H NMR(300MHz,CDCl3):6.28(t,J＝2.6Hz,2H),6.19(t,J＝2.6Hz,2H),3.31(t,6.6Hz,2H),2.62(t,J＝8Hz),1.7-1.3(m,8H),1.17(s,9H).
13C NMR(CDCl3):135.09,116.66,112.28,72.42,61.52,30.66,30.61,30.14,29.18,27.58,26.00.
Preparation of example 3
Step 1) drying of the support
Silica (SYLOPOL 948 manufactured by Grace Davison) was dehydrated at 400 ℃ for 15 hours in a vacuum state.
Step 2) preparation of Supported vectors
10g of the dried silica of step 1 are introduced into a glass reactor into which 100mL of toluene are additionally added and stirred. To this was added 50mL of a 10 wt% Methylaluminoxane (MAO)/toluene solution, and the mixture was slowly reacted with stirring at 40 ℃. Thereafter, the reaction solution was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed under reduced pressure. 100mL of toluene was further added thereto, and 0.25mmol of the metallocene catalyst prepared in preparation example 1 dissolved in toluene was added together and reacted for 1 hour. After completion of the reaction, 0.25mmol of the metallocene catalyst prepared in preparation example 2 dissolved in toluene was added and the reaction was further carried out for 1 hour. After the reaction was completed, the stirring was stopped, toluene was removed by layer separation, and 1.0mmol of anilinium borate (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, AB) was added thereto, and stirred for 1 hour. Toluene was then removed under reduced pressure at 50 ℃ to give a supported catalyst.
Example 1: ethylene/alpha-olefin copolymer
50mg of the supported catalyst prepared in preparation example 3 was weighed in a dry box and introduced into a 50mL glass bottle. The bottle was sealed with a rubber septum and removed from the dry box to prepare the catalyst for injection. The polymerization was carried out in a 2L metal alloy reactor equipped with a mechanical stirrer and capable of controlling the temperature and being used under high pressure.
1L of hexane containing 1.0mmol of triethylaluminum and 1-hexene (5mL) was introduced into the reactor, and then the prepared supported catalyst was introduced thereinto without contacting with air. Then, at 9Kgf/cm2While continuously supplying a gaseous ethylene monomer under a pressure of (1) at 80 ℃ for 1 hour. The polymerization was terminated by stopping the stirring and discharging the ethylene. After most of the polymerization solvent thus obtained was filtered off, the resulting polymer was dried in a vacuum oven at 80 ℃ for 4 hours.
Example 2: ethylene/alpha-olefin copolymer
An ethylene/α -olefin copolymer was prepared in the same manner as in example 1, except that the amount of added 1-hexene was less than 5 mL.
Comparative examples
The following products were used as comparative examples.
Comparative example 1: 2010J (Letian chemical)
Comparative example 2: LUTENE-H ME 8000(LG chemical Co., Ltd.)
Comparative example 3: RigidexHD 6070UA (Enlishi)
Experimental examples: evaluation of physical Properties of Polymer
The physical properties of the polymers prepared in the above examples and comparative examples were evaluated in the following manner.
1) Density: ASTM 1505
2) Melt flow index (MFR, 5kg/2.16 kg): measurement temperature 190 ℃, ASTM D1238
3)MFRR(MFR5/MFR2.16)：MFR5Melt index (MI, load: 5kg) divided by MFR2.16(MI, load 2.16 kg).
4) Mn, Mw, MWD, GPC curve: the samples were melted at 160 ℃ using PL-SP260 and pretreated for 10 hours in 1,2, 4-trichlorobenzene containing 0.0125% BHT, and the number average molecular weight and weight average molecular weight were determined using PL-GPC220 at a temperature of 160 ℃. The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.
5) Spherulite size: the surface of the sample was observed with a microscope. Specifically, the diameter of spherulites was measured after the ethylene/alpha-olefin copolymer was completely melted at 190 ℃ and then reached the crystallization temperature at a rate of 10 ℃/min. Here, the diameter of the spherulites is a size at which the respective spherulites overlap according to growth of the spherulites.
6) Half crystallization time (. tau. 1/2 at 123 ℃): differential Scanning Calorimetry (DSC) was used to determine the half-crystallization time, which is the time at which the ethylene/alpha-olefin copolymer completely melts at 190 ℃ and quenches (80 ℃/min) until half of the peak heat value occurs after the crystallization temperature (123 ℃).
The results are shown in table 1 below. In addition, the observation results of spherulites of each copolymer are shown in FIGS. 1 to 3.
[ Table 1]
Figure GDA0002655241330000221
As shown in the above table 1, it was confirmed that the size of the spherulites according to the example of the present invention was less than 20 μm, whereas the size of the spherulites of the comparative example exceeded 20 μm. It was also confirmed that the semi-crystallization speed was significantly faster than that of comparative example 3, in which the molecular weight and the molecular weight distribution were similar to those of the inventive example.

Claims (5)

1. An ethylene/α -olefin copolymer having:
a weight average molecular weight of 50,000 to 150,000g/mol,
a molecular weight distribution Mw/Mn of from 3 to 8,
0.940 to 0.970g/cm3The density of (a) of (b),
melt flow index MFR determined according to ASTM D1238 at 190 ℃ under a load of 2.16kg2.16Is the range of 4 to 8, and the content of the active ingredient,
a spherulite diameter of 20 μm or less, and
a semi-crystallization time measured at 123 ℃ of 6 minutes or less,
wherein the metallocene compound is represented by the following chemical formula 1; and polymerizing ethylene and an α -olefin in the presence of one or more second metallocene compounds selected from the group consisting of compounds represented by the following chemical formulas 3 to 5 to prepare the ethylene/α -olefin copolymer:
[ chemical formula 1]
Figure FDA0002655241320000011
In the chemical formula 1, the first and second,
a is hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-20Aryl radical, C7-20Alkylaryl group, C7-20Arylalkyl radical, C1-20Alkoxy radical, C2-20Alkoxyalkyl group, C3-20Heterocycloalkyl or C5-20A heteroaryl group;
d is-O-, -S-, -N (R) -or-Si (R) (R ') -, wherein R and R' are the same or different from each other and are each independently hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl or C6-20An aryl group;
l is C1-10A linear or branched alkylene group;
b is carbon, silicon or germanium;
q is hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-20Aryl radical, C7-20Alkylaryl or C7-20An arylalkyl group;
m is a group 4 transition metal;
X1and X2Are identical or different from each other and are each independently halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-20Aryl, nitro, amido, C1-20Alkylsilyl group, C1-20Alkoxy or C1-20A sulfonate group;
C1and C2Are identical to or different from each other, and are each independently represented by one of the following chemical formulae 2a, 2b or 2C, with the exception of C1And C2Both in the case of chemical formula 2c,
[ chemical formula 2a ]
Figure FDA0002655241320000021
[ chemical formula 2b ]
Figure FDA0002655241320000022
[ chemical formula 2c ]
Figure FDA0002655241320000023
In chemical formulas 2a, 2b and 2c, R1To R17And R1' to R9' the same or different from each other, and each independently is hydrogen, halogen, C1-20Alkyl radical, C2-20Alkenyl radical, C1-20Alkylsilyl group, C1-20Silylalkyl group, C1-20Alkoxysilyl group, C1-20Alkoxy radical, C6-20Aryl radical, C7-20Alkylaryl or C7-20Arylalkyl radical, andtwo or more adjacent R10To R17Are linked to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
[ chemical formula 3]
(Cp1Ra)n(Cp2Rb)M1Z1 3-n
In the chemical formula 3, the first and second,
M1is a group 4 transition metal;
Cp1and Cp2The same or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl group, indenyl group, 4,5,6, 7-tetrahydro-1-indenyl group and fluorenyl group, which may be substituted with hydrocarbon having 1 to 20 carbon atoms;
Raand RbAre identical or different from each other and are each independently hydrogen, C1-20Alkyl radical, C1-10Alkoxy radical, C2-20Alkoxyalkyl group, C6-20Aryl radical, C6-10Aryloxy radical, C2-20Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C8-40Arylalkenyl or C2-10An alkynyl group;
Z1is a halogen atom, C1-20Alkyl radical, C2-10Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C6-20Aryl, substituted or unsubstituted C1-20Alkylene group, substituted or unsubstituted amino group, C2-20Alkyl alkoxy or C7-40An arylalkoxy group;
n is 1 or 0;
[ chemical formula 4]
(Cp3Rc)mB1(Cp4Rd)M2Z2 3-m
In the chemical formula 4, the first and second organic solvents,
M2is a group 4 transition metal;
Cp3and Cp4Are identical or different from each other and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6, 7-tetrahydro-1-indenyl and fluorenylAny of the cyclopentadienyl, indenyl, 4,5,6, 7-tetrahydro-1-indenyl, and fluorenyl groups may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
Rcand RdAre identical or different from each other and are each independently hydrogen, C1-20Alkyl radical, C1-10Alkoxy radical, C2-20Alkoxyalkyl group, C6-20Aryl radical, C6-10Aryloxy radical, C2-20Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C8-40Arylalkenyl or C2-10An alkynyl group;
Z2is a halogen atom, C1-20Alkyl radical, C2-10Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C6-20Aryl, substituted or unsubstituted C1-20Alkylene group, substituted or unsubstituted amino group, C2-20Alkyl alkoxy or C7-40An arylalkoxy group;
B1to make Cp3RcRing and Cp4RdRing crosslinking or bringing together a Cp4RdRing and M2At least one of cross-linked free radical-containing carbon, germanium, silicon, phosphorus, or nitrogen atoms, combinations thereof;
m is 1 or 0;
[ chemical formula 5]
(Cp5Re)B2(J)M3Z3 2
In the chemical formula 5, the first and second organic solvents,
M3is a group 4 transition metal;
Cp5is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6, 7-tetrahydro-1-indenyl and fluorenyl, which may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
Reis hydrogen, C1-20Alkyl radical, C1-10Alkoxy radical, C2-20Alkoxyalkyl group, C6-20Aryl radical, C6-10Aryloxy radical, C2-20Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C8-40Aryl radicalsAlkenyl or C2-10An alkynyl group;
Z3is a halogen atom, C1-20Alkyl radical, C2-10Alkenyl radical, C7-40Alkylaryl group, C7-40Arylalkyl radical, C6-20Aryl, substituted or unsubstituted C1-20Alkylene group, substituted or unsubstituted amino group, C2-20Alkyl alkoxy or C7-40An arylalkoxy group;
B2to make Cp5ReAt least one of a radical-containing carbon, germanium, silicon, phosphorus, or nitrogen atom, or a combination thereof, with the ring crosslinked with J;
j is selected from NRf、O、PRfAnd any of S, and RfIs C1-20Alkyl, aryl, substituted alkyl or substituted aryl.
2. The ethylene/alpha-olefin copolymer according to claim 1,
wherein the polymer chains of the ethylene/alpha-olefin copolymer aggregate into bundles to form platelets, and the spherulites are determined by the three-dimensional growth of the platelets.
3. The ethylene/alpha-olefin copolymer according to claim 1,
wherein the semicrystallization time measured at 123 ℃ is 5 minutes or less.
4. The ethylene/alpha-olefin copolymer according to claim 1,
wherein, MFRR5/2.16Is a mixture of a water-soluble polymer and a water-soluble polymer, and is in a range of 3 to 8,
wherein the MFRR5/2.16Is the value of the melt flow index measured at 190 ℃ under a load of 5kg divided by the melt flow index measured at 190 ℃ under a load of 2.16kg, according to ASTM D1238.
5. The ethylene/alpha-olefin copolymer according to claim 1,
wherein the alpha-olefin is one or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene.
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